Thin film forming apparatus and transparent conductive film

ABSTRACT

A thin film forming apparatus including: a first chamber configured to generate a mist of a dispersion liquid, and including an outlet; a second chamber configured to receive the generated mist from the first chamber and collect particles of the generated mist having a size greater than a predetermined value, and including an inlet provided on a top of the second chamber and connected to the outlet of the first chamber, and an outlet provided on the top of the second chamber and configured to transfer, as homogenized mist, particles of the generated mist having a size less than or equal to the predetermined value due to the effect of gravity on the particles of the mist; and a third chamber configured to receive the homogenized mist from the second chamber, and including an inlet connected to the outlet of the second chamber.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 16/407,344, filed on May 9, 2019, which is a divisionalapplication of U.S. patent application Ser. No. 15/097,956, filed onApr. 13, 2016, which is a § 111(a) by-pass continuation application,which claims the benefit under 35 U.S.C. § 371 of PCT InternationalPatent Application No. PCT/JP2014/78064, filed Oct. 22, 2014, whichclaims the foreign priority benefit under 35 U.S.C. § 119 of JapanesePatent Application No. 2013-225549, filed Oct. 30, 2013, the contents ofwhich are incorporated herein by reference.

FIELD

The present invention relates to a method of manufacturing a thin filmand to a transparent conductive film.

BACKGROUND

A transparent conductive film formed of indium tin oxide (ITO), zincoxide (ZnO), or the like is widely used for a transparent electrode of aliquid crystal display or a solar cell. Such a transparent conductivefilm is typically formed by sputtering.

As a method other than sputtering, for example, in International PatentWO2011/151889A, there is disclosed formation of a metal oxide film using“an apparatus configured to form a metal oxide film, including a firstcontainer (5A) holding a material solution (10) containing a metal, asecond container (5B, 18) holding hydrogen peroxide, a reactioncontainer (1) having a substrate (2) arranged therein and having aheater (3) configured to heat the substrate, a first pathway (L1)connecting the first container and the reaction container, for supplyingthe material solution from the first container to the reactioncontainer, and a second pathway (L2) connecting the second container andthe reaction container, for supplying the hydrogen peroxide from thesecond container to the reaction container” In the film formingapparatus disclosed in International Patent WP2011/151889A, the materialsolution containing the metal and the hydrogen peroxide are reacted witheach other on the heated substrate to form the metal oxide film.

It is an object of the present invention to provide a novel method ofobtaining a thin film to replace the related art described above.

SUMMARY

One embodiment of the present invention has been made in order to attainthe above-mentioned object, and according to the one embodiment of thepresent invention, there is provided a method of manufacturing a thinfilm, including: generating mist of a dispersion liquid containing fineparticles; supplying the generated mist of the dispersion liquid onto asubstrate; and drying the dispersion liquid supplied onto the substrate.

Further, in the method of manufacturing a thin film according to the oneembodiment of the present invention, the fine particles contained in thegenerated mist of the dispersion liquid may each have a particle size of100 nm or less.

Further, in the method of manufacturing a thin film according to the oneembodiment of the present invention, the substrate may include a resinand have flexibility.

Further, in the method of manufacturing a thin film according to the oneembodiment of the present invention, the drying the dispersion liquidmay be performed at a temperature that is lower than a softening pointof the substrate.

Further, in the method of manufacturing a thin film according to the oneembodiment of the present invention, the drying the dispersion liquidmay be performed at a temperature of 10° C. or higher and 40° C. orlower.

Further, the method of manufacturing a thin film according to the oneembodiment of the present invention may further include forming, on thesubstrate, a hydrophilic/water-repellent pattern including a hydrophilicportion and a water-repellent portion, and the supplying the generatedmist may be performed to the substrate having thehydrophilic/water-repellent pattern formed thereon in the forming ahydrophilic/water-repellent pattern.

Further, the method of manufacturing a thin film according to the oneembodiment of the present invention may further include, after thedrying the dispersion liquid, radiating an ultraviolet ray to thesubstrate, and the supplying the generated mist may be performed againto the substrate to which the ultraviolet ray is radiated in theradiating an ultraviolet ray.

Further, in the method of manufacturing a thin film according to the oneembodiment of the present invention, in the supplying the generatedmist, the fine particles contained in the mist that is supplied beforethe radiating an ultraviolet ray and the fine particles contained in themist that is supplied after the radiating an ultraviolet ray may bedifferent.

Further, in the method of manufacturing a thin film according to the oneembodiment of the present invention, the ultraviolet ray radiated in theradiating an ultraviolet ray may at least have a wavelength of 200 nm orless.

Further, in the method of manufacturing a thin film according to the oneembodiment of the present invention, in the supplying the generatedmist, the substrate may be tilted from a horizontal plane.

Further, in the method of manufacturing a thin film according to the oneembodiment of the present invention, in the supplying the generatedmist, the substrate maybe tilted from a plane orthogonal to a directionof the supply.

Further, in the method of manufacturing a thin film according to the oneembodiment of the present invention, the fine particles may be metaloxide fine particles including any one of indium, zinc, tin, andtitanium.

Further, according to another embodiment of the present invention, thereis provided a transparent conductive film, which is manufactured by theabove-mentioned method of manufacturing a thin film.

It is possible to provide a novel method of obtaining a thin film toreplace the related art.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is sectional views for illustrating an exemplary method offorming a metal oxide film according to an embodiment of the presentinvention.

FIG. 2 is an illustration of an exemplary film forming apparatusaccording to the embodiment.

FIG. 3 is sectional views (part one) for illustrating an exemplarymethod of manufacturing a conductive film according to a modificationexample of the embodiment.

FIG. 4 is sectional views (part two) for illustrating the exemplarymethod of manufacturing a conductive film according to the modificationexample.

FIG. 5 is a schematic view of a roll-to-roll manufacturing apparatus.

FIG. 6 is a graph for showing sheet resistance versus heating/dryingtemperature.

FIG. 7 is a SEM image of an obtained ITO film.

FIG. 8 is a table for showing sheet resistances of the obtained metaloxide films for various heating/drying temperatures.

FIG. 9 is a SEM image of an obtained ITO film of a comparative example.

FIG. 10 is a table for showing surface resistance values and visiblelight transmittances of obtained GZO films.

FIG. 11 is a SEM image of an obtained GZO film.

FIG. 12 is a graph for showing a result of analysis of an obtained GZOfilm by EDX.

FIG. 13 is SEM images of obtained GZO films.

FIG. 14 is a table for showing a relationship between a substratetemperature in film formation and a surface resistance.

FIG. 15 is a SEM image of an ITO film on a water-repellent patternedsubstrate.

FIG. 16 is a SEM image of a GZO film on a water-repellent patternedsubstrate.

FIG. 17 is a SEM image of a substrate heated to 60° C.

FIG. 18 is a SEM image of a substrate heated to 80° C.

FIG. 19 is a SEM image of an obtained ITO film.

DESCRIPTION OF EMBODIMENTS

An exemplary embodiment of the present invention is described below withreference to the attached drawings.

FIG. 1 is sectional views for illustrating an exemplary method offorming a thin film according to this embodiment.

(First Step)

First, a substrate 10 is prepared. As a material of the substrate 10,substrate materials commonly used can be used. For example, glass,polyethylene terephthalate (PET), polyethylene naphthalate (PEN),polyether sulfone (PES), polyether imide, polyether ether ketone,polyphenylene sulfide, polyacrylate, polyimide, polycarbonate (PC),cellulose triacetate (TAC), or cellulose acetate propionate (CAP) can beused.

The substrate 10 is cleaned as necessary. As a cleaning method, ageneral method such as ultrasonic cleaning can be used. After that, anultraviolet (UV) ray is radiated to the substrate 10. In radiating a UVray, a general UV radiation apparatus is used, and it is desired that anultraviolet ray having a wavelength of 200 nm or less (for example, from10 nm to 200 nm) be radiated. The radiation of a UV ray removes animpurity on a surface of the substrate 10 to hydrophilize the surface.

(Second Step)

Then, through spraying mist of a dispersion liquid containing fineparticles onto the substrate 10, a metal oxide film 2 is formed.

FIG. 2 is an illustration of an exemplary film forming apparatusaccording to this embodiment. The film forming apparatus includes afirst chamber configured to generate mist containing fine particles, asecond chamber as a mist trap, which is configured to homogenize themist, and a third chamber configured to spray the mist onto thesubstrate 10.

The first chamber holds a material solution 5 as a dispersion liquid inwhich fine particles are dispersed in a dispersion medium. As the fineparticles, conductive metal fine particles of indium, zinc, tin,titanium, or the like, or metal oxide fine particles of at least onethereof can be used. These may be solely used, or two or more thereofmay be arbitrarily used in combination. The fine particles are nanofineparticles having a particle size of from 1 nm to 100 nm. Note that, asthe particle size, for example, an average of major axes and minor axesof fine particles determined from a SEM image can be used. Note that, inthis embodiment, description is made assuming that metal oxide fineparticles are used as the fine particles.

The dispersion medium may be any type of medium insofar as the fineparticles can be dispersed therein, and water, an alcohol such asisopropyl alcohol (IPA) or ethanol, or a mixture thereof can be used.Note that, air 22 for forming a flow path of the mist is flowed into thefirst chamber.

The first chamber holds an ultrasonic vibrator 21 as well. Theultrasonic vibrator 21 generates the mist of the dispersion liquidcontaining the metal oxide fine particles. It is desired that the misthave a particle size of 10 μm or less (for example, from 1 μm to 10 μm).The mist generated in the first chamber is sent to the second chambervia a tube arranged at the first chamber. In the second chamber, excessmist accumulates in a lower portion of the chamber, and mist with ahomogenized particle size is sent to the third chamber via a tubearranged at the second chamber. It is desired that mist having aparticle size of 5 μm or less (for example, from 1 μm to 5 μm) be sentfrom the second chamber to the third chamber.

The substrate 10 is set in the third chamber, and the mist sent from thesecond chamber is sprayed onto the substrate 10. The mist is sprayedonto the substrate 10 for a predetermined time in the third chamber.Through vaporization of the dispersion medium in the mist attached tothe substrate 10, the metal oxide film is formed on the surface of thesubstrate 10. Note that, when a fixed time elapses after the spray, newmist attaches onto the substrate 10 before the mist is vaporized, andthus, the dispersion liquid that becomes liquid droplets flows down, anda uniform metal oxide film is no longer formed on the substrate 10. Apoint in time at which the spraying of the mist onto the substrate 10 isstopped may be a point in time at which the mist including the metaloxide fine particles is liquefied to flow down from the substrate 10, ormay be a point in time at which a metal oxide film having a desiredthickness is formed on the substrate 10.

When the substrate 10 is excessively heated in the third chamber, thesubstrate 10 may be softened to be deformed. Therefore, in the thirdchamber, it is desired that the mist be sprayed at a temperature lowerthan a softening point of the substrate 10 to form the metal oxide film.Further, when the substrate 10 is heated to a predetermined temperatureor higher when the mist is sprayed thereonto, the metal oxide fineparticles attached to the substrate 10 coagulate to form a metal oxidefilm having a high resistance value. Therefore, it is further desiredthat the mist be sprayed at a temperature that is equal to or lower than40° C. (for example, from 10° C. to 40° C.) to form the metal oxidefilm.

Note that, the softening point as used herein means a temperature atwhich, when the substrate is heated thereto, the substrate is softenedto start to be deformed, and can be determined by, for example, atesting method in conformance with JIS K7207 (method A).

As described in detail below, when a metal oxide film is selectivelyformed on the substrate 10, by selectively forming a water-repellentfilm on the substrate 10 in advance, the mist is attached to ahydrophilic portion. At this time, if the substrate 10 is placed so asto be level, the dispersion liquid attached to a water-repellent portionis not repelled, and thus, the metal oxide film cannot be selectivelyformed. Therefore, it is desired that, in the third chamber, the mist besprayed onto the substrate 10 that is tilted from a horizontal plane.

Similarly, it is desired that, in the third chamber, the mist be sprayedonto the substrate 10 that is tilted from a plane orthogonal to adirection of the spraying of the mist. This is for the purpose ofremoving excess metal oxide fine particles attached to thewater-repellent portion due to momentum of the sprayed mist.

Note that, the mist trap in the second chamber of the film formingapparatus may be omitted. This enables formation of the metal oxide filmon the substrate with a simpler apparatus.

Further, with regard to a method of generating the mist, other thangeneration using the ultrasonic vibrator 21 described above, anelectrostatic method in which the mist is generated through directapplication of a voltage to a thin tube for spraying liquid droplets, apressurizing method in which generated mist is dispersed by colliding,with a liquid, a gas having an increased flow velocity with pressureapplied thereto, a rotary disk method in which liquid droplets aredropped onto a disk rotating at high speed and generated mist isdispersed by a centrifugal force, an orifice vibration method in which,when liquid droplets are passed through microsized holes formed in anorifice plate, the liquid droplets are cut by vibrations applied theretoby a piezoelectric element or the like, thereby generating microsizedliquid droplets, or the like can be used. The method of generating themist is selected as appropriate among these in accordance with the cost,the performance, or the like. It is to be understood that a plurality ofmethods may be used in combination to generate the mist.

(Third Step)

Description is made again with reference to FIG. 1. After that, thesubstrate 10 having the metal oxide film 2 formed thereon is heated tobe dried. Similarly to the case described above, it is desired that theheating temperature at this time be lower than the softening point ofthe substrate 10. The heating may be performed in a low vacuum of about30 Pa, or may be performed in an atmosphere of Ar gas. An appropriatethermal condition is used depending on a condition of the film formationor the like. Note that, in this step, the drying is not necessarilyrequired to be performed by heating. For example, the drying may beperformed by setting the substrate 10 at room temperature for apredetermined time.

Note that, the first step described above is not an indispensable step.The first step is a step as a pretreatment for the mist to be attachedonto the substrate 10 in the second step. It is enough that the mist isattached onto the substrate 10, and a method of attaining this is notlimited.

Through the processes described above, the metal oxide film is formed onthe substrate 10. By repeating the processes from the first step to thethird step as necessary, a metal oxide film as a second layer can beobtained. In this case, the first step of cleaning the substrate can beomitted. Note that, by using, as metal oxide fine particles included inthe mist of the second layer, the same material as that of the metaloxide fine particles included in the mist of the first layer, a metaloxide film having a sufficient thickness can be obtained. Alternatively,by using different materials for the metal oxide film for the firstchamber and for the metal oxide film for the second chamber, differentconductive films can be formed in accordance with the use or the targetthereof.

As described above, according to this embodiment, in the step of formingthe thin film, the film is formed without heating the substrate.Therefore, a metal oxide film having a low resistance value can beobtained. Further, a film can be effectively formed on a substrate thatis sensitive to heat.

MODIFICATION EXAMPLE

Next, a modification example of this embodiment is described.

FIG. 3 is sectional views for illustrating an exemplary method ofmanufacturing a conductive film according to this modification example.In this modification example, the metal oxide film formed according tothe embodiment described above is used to manufacture the conductivefilm. The manufactured conductive film is used in a touch panel or thelike as a capacitance switch.

(First Step)

First, a UV ray is radiated to the substrate 10. The UV radiation is forthe purpose of removing an impurity on the substrate 10. Note that, thefirst step may be omitted.

(Second Step)

Next, a resist 11 is applied onto the substrate 10. The resist 11 is ageneral photosensitive material used as a photoresist. In theapplication, a publicly known application method such as spin coating,dip coating, or spraying can be used.

(Third Step)

Next, the substrate 10 is selectively exposed. Specifically, a photomaskthat is patterned as desired in advance is used to selectively exposepart of the resist 11 on the substrate 10. By developing the substrate10 after that, the resist 11 that is patterned into a desired shape isobtained. Note that, here, for convenience sake, a case in which aphotomask that selectively masks the substrate 10 in an x directionthereof (side to side direction in FIG. 3) is used in the exposure isdescribed.

(Fourth Step)

Next, a water-repellent film 3 is formed on the substrate 10. As thewater-repellent film 3, an existing material such as a fluorine-basedwater repellent is used. As the water-repellent film 3, for example,3M_(TM)Novec_(TM)EGC-1720 (manufactured by 3M Japan Limited) can beused. As a method of forming the water-repellent film 3, similarly tothe case of the application of the resist 11 described above, anexisting film forming method is used to form the film.

(Fifth Step)

Next, the resist 11 on the substrate 10 is peeled. The resist 11 ispeeled using an existing peeling liquid such as acetone. By peeling theresist 11, the water-repellent film formed on the resist 11 is peeled aswell. In this way, the water-repellent film 3 that is patterned asdesired can be obtained.

(Sixth Step)

Next, the mist of the dispersion liquid containing the metal oxide fineparticles is sprayed onto the substrate 10 to form the metal oxide film2. Specifically, the film forming apparatus illustrated in FIG. 2 isused to spray the mist, thereby forming the film. The water-repellentfilm 3 is selectively formed on the substrate 10, and thus, theliquefied dispersion liquid attaches to a portion of the substrate 10that has no water-repellent film 3 formed thereon, that is, to thehydrophilic portion, and the metal oxide film 2 is selectively formed.Note that, the dispersion liquid that temporarily attaches to thewater-repellent portion flows down through the water-repellent portiondue to the tilt of the substrate 10 to attach to an adjacent hydrophilicportion, or flows down through the substrate 10 to accumulate at abottom portion of the third chamber. The metal oxide film 2 formed onthe substrate 10 is, after that, heated to be dried.

(Seventh Step)

Next, an insulating film 4 is formed on the substrate 10. Note that, aUV ray can be radiated to the substrate before the insulating film 4 isformed. This is for the purpose of, by radiating a UV ray to thewater-repellent film 3, reducing the water repellent property to helpformation of the insulating film 4. However, when, for example, a highlyviscous material such as an organic material is used to form theinsulating film 4, it is not necessary to consider the effect of thewater repellent property of the water-repellent film 3, and thus, it isnot necessary to radiate a UV ray. Taking into consideration of thematerial of the insulating film 4 and the like, a UV ray is radiated asnecessary, and after that, the insulating film 4 is formed on thesubstrate 10.

The insulating film 4 is formed on the water-repellent film 3 and on themetal oxide film 2. As the insulating film 4, for example, anonconductive material such as SnO₂ is used. As a method of forming theinsulating film 4, an existing method such as spin coating, bar coating,or dip coating is used to apply a predetermined material on an entiresurface to form the film.

FIG. 4 is sectional views (part two) for illustrating the exemplarymethod of manufacturing a conductive film according to this modificationexample.

(Eighth Step)

Next, a UV ray is radiated to the substrate 10. A UV ray is radiated forthe purpose of facilitating formation of the metal oxide film as thesecond layer on the insulating film 4.

(Ninth Step)

Next, the resist 11 is applied to the substrate 10. The application ofthe resist 11 is performed similarly to that in the second step.

(Tenth Step)

Then, the substrate 10 is selectively exposed and developed. In thethird step, the exposure was performed using a photomask thatselectively masks the substrate 10 in the x direction thereof. In thisstep, description is made of a case in which the exposure is performedusing a photomask that selectively masks the substrate 10 in a ydirection thereof (direction orthogonal to a side to side direction inFIG. 4). The exposure and the development are performed similarly tothose in the third step.

(Eleventh and Twelfth Steps)

Next, the water-repellent film 3 is applied to the substrate 10. Afterthat, the resist 11 that remains on the substrate 10 is peeled togetherwith the water-repellent film 3 formed on the resist 11. The eleventhstep and the twelfth step are performed similarly to the fourth step andthe fifth step, respectively.

(Thirteenth Step)

Then, the metal oxide film 2 as the second layer is formed on thesubstrate 10. In forming the metal oxide film 2, similarly to the caseof the sixth step, the film forming apparatus illustrated in FIG. 2 isused. After that, the metal oxide film 2 is dried. Note that, in FIG. 4,as the second layer, the metal oxide film 2 is selectively formed in they direction of the substrate 10, and thus, in the sectional views of thesubstrate 10, the metal oxide film 2 as the second layer is illustratedas if being formed on the entire surface of the substrate 10.

(Fourteenth Step)

Then, the insulating film 4 is formed on the substrate 10. Theinsulating film 4 is formed on the metal oxide film 2 formed in thethirteenth step. The insulating film 4 is formed by a film formingmethod similar to that in the seventh step using a material similar tothat used in the seventh step.

As described above, in this embodiment, by forming the metal oxide filmhaving a patterned shape and forming a protective layer that is theinsulating film on an outermost surface, a touch panel that operates inaccordance with change in capacitance can be formed. Further, by formingthe metal oxide film using the film forming apparatus described above, ametal oxide film having a lower resistance value and a highertransparency compared with a general metal oxide film can be obtained.

FIG. 5 is a schematic view of a roll-to-roll manufacturing apparatus. Inthis manufacturing apparatus, when a film 20 formed in a roll is set onone side of the apparatus, the film 20 having a metal oxide film formedthereon is discharged from another side of the apparatus. Note that, thefilm 20 is used as the substrate in the embodiment described above, andcontains a resin and has flexibility.

(Step 1: Cleaning)

First, the film 20 is cleaned. As a method of the cleaning, a generalmethod such as ultrasonic cleaning is used.

(Step 2: UV Radiation)

Then, a UV ray is radiated to the film 20. As described above, inradiating a UV ray, a general UV radiation apparatus is used, and it isdesired that a UV ray having a wavelength of 200 nm or less be radiated.

(Step 3: Mist Spraying)

Then, the mist generated from the dispersion liquid in which the metaloxide fine particles are dispersed is sprayed onto the film 20. A filmforming apparatus used in Step 3 is the film forming apparatus describedwith reference to FIG. 2. Note that, as described above, the filmforming apparatus forms the metal oxide film at a temperature lower thanthe softening point of the film 20. In this step, the film 20 having themetal oxide film attached thereto can be obtained.

(Step 4: Heating)

Then, the film 20 is heated to dry the metal oxide film attached to thefilm 20 in Step 3. Note that, as described above, a temperature used inthe heating is lower than the softening point of the film 20.

(Step 5: Slow Cooling)

Then, the film 20 is gradually cooled. In this step, a cooling apparatusmay be used to cool the film 20.

(Step 6: UV Radiation)

In this manufacturing apparatus, the metal oxide film as the secondlayer is formed on the formed metal oxide film. Therefore, in this step,a UV ray is radiated to the film 20 to remove an impurity, therebyimproving the hydrophilic property. Note that, when formation of themetal oxide film ends when the first layer is formed, this step andsubsequent steps are omitted.

(Step 7: Mist Spraying)

Then, the mist is sprayed onto the film 20. In this step, similarly tothe case of Step 3, the film forming apparatus illustrated in FIG. 2 isused to form the metal oxide film on the film 20. In this step, themetal oxide film as the second layer is formed on the metal oxide filmas the first layer formed in Step 3.

(Step 8: Heating)

Then, the film 20 is heated to dry the metal oxide film attached to thefilm 20 in Step 8.

(Step 9: Slow Cooling)

Then, the film 20 is gradually cooled.

As described above, by using the roll-to-roll manufacturing apparatus,the metal oxide film can be formed continuously on the substrate formedin a roll. Further, a temperature lower than the softening point of thesubstrate containing a resin and having flexibility can be used to forma high performance metal oxide film.

The embodiment of the present invention is hereinafter more specificallydescribed by way of Examples. However, the present invention is notlimited to the following Examples.

EXAMPLE 1

First, a water dispersion liquid (NanoTek Slurry manufactured by C. I.Kasei Company, Limited) containing ITO fine particles was prepared. TheITO fine particles had a particle size of from 10 nm to 50 nm, and anaverage particle size was 30 nm. Materials and particle sizes of ITOfine particles used in other examples described below are similar tothose in this example. Further, a concentration of the metal oxide fineparticles in the dispersion liquid was 15 wt %. The prepared dispersionliquid was put in the first chamber of the film forming apparatusdescribed above, and a voltage of 2.4 MHz was applied by the ultrasonicvibrator (manufactured by HONDA ELECTRONICS Co., LTD.) to generate themist. The obtained mist was sent to the vicinity of the substrate in asecond chamber by causing air to flow into the first chamber. Note that,in the film forming apparatus used in this example, the second chamberas the mist trap is omitted. Therefore, the mist was sprayed onto thesubstrate in the second chamber. Note that, as the substrate, a sodalime glass substrate was used.

In the second chamber, the mist continued to be sprayed onto thesubstrate for five minutes under a state in which the substrate wastilted from the horizontal plane and the substrate was tilted from theplane orthogonal to the direction of the spraying of the mist by 45degrees. At this time, the substrate was not heated, and the sprayingwas performed at room temperature.

After the mist was sprayed onto the substrate, an infrared lamp heatingapparatus was used to perform the heating in different patterns of from100° C. to 200° C. The heating was performed for ten minutes in a lowvacuum of about 30 Pa using a rotary pump, or in an atmosphere of aninert gas (Ar).

After that, a UV ray (mixture of 254 nm and 185 nm) was radiated to adried surface of the ITO film. Then, subsequently thereto, similarly tothe case described above, the substrate was set in the second chamber ofthe film forming apparatus, and the mist continued to be sprayed forfive minutes at room temperature. After that, similarly to the casedescribed above, by performing the heating for ten minutes using theinfrared lamp heating apparatus, the substrate was dried.

(Evaluation)

FIG. 6 is a graph for showing sheet resistance versus heating/dryingtemperature. Note that, the sheet resistance shown in this figure wasmeasured by a four probe method. With reference to data shown in FIG. 6,it was found that, in a low temperature region of 200° C. or lower,which is temperature at which the film that formed the substrate isheat-resistant, sheet resistances of less than 1,000 Ω/sq. was obtained.

Further, when the process under atmospheric pressure in an atmosphere ofthe inert gas (Ar) and the process in the low vacuum of about 30 Pa werestudied, it was found that the process in the low vacuum exhibited lowerresistances in a temperature region of 150° C. or higher.

Note that, when transmittances of the obtained samples were measuredusing a spectrophotometer at a wavelength of 550 nm, all the samplesshown in FIG. 6 exhibited visible light transmittances of 80% or higher.p FIG. 7 is a SEM image of an obtained ITO film. FIG. 7 is an image of asurface of a sample in the case in which the heating temperature whenthe sample was dried was 200° C., which was observed under a scanningelectron microscope (SEM). No irregularities are observed on the surfaceand smoothness can be confirmed.

As described above, it was clarified that the metal oxide films formedusing the mist exhibited low sheet resistances. Further, it was foundthat metal oxide films that did not lose a light transmitting propertyand that had smoothness was formed.

EXAMPLE 2

A water dispersion liquid containing ITO fine particles was put in thefirst chamber of the film forming apparatus described above that did nothave the mist trap, and a voltage of 2.4 MHz was applied by theultrasonic vibrator (manufactured by HONDA ELECTRONICS Co., LTD.) togenerate the mist. The obtained mist was sent to the vicinity of thesubstrate in the second chamber by causing air to flow into the firstchamber. Note that, as the substrate, a soda lime glass substrate wasused.

In the second chamber, the mist continued to be sprayed onto thesubstrate for five minutes under a state in which the substrate wastilted from the horizontal plane and the substrate was tilted from theplane orthogonal to the direction of the spraying of the mist. At thistime, substrates were prepared having different substrate temperaturesthat were set to be from 20° C. to 200° C. After that, the substrateswere dried at room temperature.

Sheet resistances of metal oxide films having the different substratetemperatures in the film formation that were obtained at this time weremeasured by the four probe method.

FIG. 8 is a table for showing sheet resistances of the obtained metaloxide films for the various heating/drying temperatures. With regard tosamples in which the substrate temperature in the film formation wasraised from room temperature, increase in sheet resistance, that is,reduction in electric conductivity, was confirmed. Further, with regardto samples in which the substrate was heated to a temperature of 80° C.or higher, the sheet resistances were beyond a detection limit, andthus, the measurement was impossible. Note that, the detection limit inthis measurement was 4 GΩ/sq.

As described above, when the substrate temperature in the film formationwas 60° C. or lower, a metal oxide film having electric conductivity wasobtained. Further, when the substrate temperature was 25 degrees, whichis close to room temperature, a metal oxide film having the highestelectric conductivity was obtained.

COMPARATIVE EXAMPLE 1

A water dispersion liquid containing ITO fine particles was applied ontothe substrate 10 by spin coating at 500 rpm. The application wasperformed at room temperature. After the application, the heating fordrying was performed at a temperature of 200° C. for about ten minutesin a low vacuum of about 30 Pa. After that, a UV ray (mixture of 254 nmand 185 nm) was radiated to a surface of the film. Then, subsequentlythereto, a water dispersion liquid containing ITO fine particles wasapplied at room temperature onto the substrate by spin coating at 500rpm. After the application, heating for drying was performed at atemperature of 200° C. for about ten minutes in a low vacuum of about 30Pa. Note that, as the substrate, a soda lime glass substrate was used.

When a transmittance of the obtained ITO film was measured using aspectrophotometer at a wavelength of 550 nm, the visible lighttransmittance was 68%. Further, when a sheet resistance of the obtainedITO film was measured by the four probe method, the result was 800MΩ/sq.

FIG. 9 is a result of an observation of the surface by a SEM image. Itwas confirmed that, when the film was formed using spin coating,compared with the case of the SEM image in FIG. 7 when the film wasformed using the mist, the surface was rougher. The surface resistancevalue was higher than that of the case in which the film was formedusing the mist by three orders of magnitude, and it cannot be said thatthe ITO film of this comparative example 1 is at a practical level as atransparent electrode.

Further, surface roughnesses were measured using a stylus type thicknessmeter. In Example 1, the sample which was heated and dried at 200° C.similarly to the case of this comparative example had a surfaceroughness Ra of 15 nm. On the other hand, the film obtained in thiscomparative example had a surface roughness Ra of 80 nm.

As described above, it was found that, compared with the film formed byspraying, onto the substrate, the mist of the dispersion liquidcontaining the metal oxide fine particles, the film formed by applyingthe dispersion liquid by spin coating had a rougher surface, a higherresistance value, and a lower visible light transmittance.

EXAMPLE 3

First, a water dispersion liquid (NanoTek Slurry manufactured by C. I.Kasei Company, Limited) containing GZO fine particles was prepared. TheGZO fine particles had a particle size of 10 nm to 50 nm, and an averageparticle size was 30 nm. Materials and particle sizes of GZO fineparticles used in other examples described below are similar to those inthis example. Further, a concentration of the metal oxide fine particlesin the dispersion liquid was 15 wt %.

The prepared dispersion liquid was put in the first chamber of the filmforming apparatus described above that did not have the mist trap, and avoltage of 2.4 MHz was applied by the ultrasonic vibrator (manufacturedby HONDA ELECTRONICS Co., LTD.) to generate the mist. The obtained mistwas sent to the vicinity of the substrate in the second chamber bycausing air to flow into the first chamber. Note that, as the substrate,a soda lime glass substrate was used.

In the second chamber, the mist continued to be sprayed onto thesubstrate for five minutes under a state in which the substrate wastilted from the horizontal plane and the substrate was tilted from theplane orthogonal to the direction of the spraying of the mist. At thistime, the substrate was not heated, and the spraying was performed atroom temperature.

After the mist was sprayed onto the substrate, an infrared lamp heatingapparatus was used to heat the substrate at 150° C., 175° C., and 200°C. in respective cases. The heating was performed for about ten minutesin a low vacuum of about 30 Pa for each of the heating temperatures.

After that, a UV ray (mixture of 254 nm and 185 nm) was radiated to adried surface of the GZO film. Then, subsequently thereto, similarly tothe case described above, the substrate was set in the second chamber ofthe film forming apparatus, and the mist continued to be sprayed forfive minutes at room temperature. After that, similarly to the casedescribed above, by performing the heating for ten minutes using theinfrared lamp heating apparatus, the substrate was dried.

FIG. 10 is a table for showing surface resistance values and visiblelight transmittances of the obtained GZO films. It was found that, inany of the cases in which the drying temperature was 150° C., 175° C.,and 200° C., a transparent conductive film exhibiting a transmittance of80% or higher in a visible light region was obtained.

Further, in any of the cases, the sheet resistance was 20 MΩ/sq. orless.

As described above, it was found that, even when GZO fine particles wereused as the metal oxide fine particles, a suitable metal oxide film wasobtained.

EXAMPLE 4

First, an IPA dispersion liquid (NanoTek Slurry manufactured by C. I.Kasei Company, Limited) containing GZO fine particles was prepared. Aparticle size of the GZO fine particles and a concentration of the metaloxide fine particles are similar to those in Example 3. The prepareddispersion liquid was put in the first chamber of the film formingapparatus described above that did not have the mist trap, and a voltageof 2.4 MHz was applied by the ultrasonic vibrator (manufactured by HONDAELECTRONICS Co., LTD.) to generate the mist. The obtained mist was sentto the vicinity of the substrate in the second chamber by causing air toflow into the first chamber.

After the mist was sprayed onto the substrate, an infrared lamp heatingapparatus was used to perform the heating for drying at a temperature of200° C. for ten minutes in a low vacuum of about 30 Pa. After that, a UVray (mixture of 254 nm and 185 nm) was radiated to a dried surface ofthe GZO film. Then, subsequently thereto, similarly to the casedescribed above, the substrate was set in the second chamber of the filmforming apparatus, and the mist continued to be sprayed for five minutesat room temperature. After that, similarly to the case described above,by performing the heating for ten minutes using the infrared lampheating apparatus, the substrate was dried. Note that, as the substrate,a soda lime glass substrate was used.

The obtained film had a sheet resistance of 10 MΩ/sq. and atransmittance in the visible light region was 80% or more.

FIG. 11 is a SEM image of the obtained GZO film. From the result of theSEM image, it was found that a flat film was formed.

FIG. 12 is a graph for showing a result of analysis of the obtained GZOfilm by EDX. Specifically, the obtained GZO film was line scanned byEnergy dispersive X-ray spectrometry (EDX). In FIG. 12, prominent peakswere observed for Zn and O, respectively, and it was found that theobtained film was formed of ZnO.

EXAMPLE 5

Similarly to the case of Example 3, a water dispersion liquid (NanoTekSlurry manufactured by C. I. Kasei Company, Limited) containing GZO fineparticles was prepared. The prepared dispersion liquid was put in thefirst chamber of the film forming apparatus described above that did nothave the mist trap, and a voltage of 2.4 MHz was applied by theultrasonic vibrator (manufactured by HONDA ELECTRONICS Co., LTD.) togenerate the mist. The obtained mist was sent to the vicinity of thesubstrate in the second chamber by causing air to flow into the firstchamber.

In the second chamber, the mist continued to be sprayed onto thesubstrate for five minutes under a state in which the substrate wastilted from the horizontal plane and the substrate was tilted from theplane orthogonal to the direction of the spraying of the mist. At thistime, one substrate was heated to 60° C. when the spraying wasperformed, and another substrate was heated to 80° C. when the sprayingwas performed. Note that, as the substrate, a soda lime glass substratewas used.

After that, an infrared lamp heating apparatus was used to heat thesubstrate at a temperature of 200° C. The heating was performed for tenminutes in a low vacuum of about 30 Pa. Subsequently thereto, after a UVray (mixture of 254 nm and 185 nm) was radiated to a surface of the GZOfilm, similarly to the case described above, the substrate was set inthe second chamber of the film forming apparatus, and similarly, themist continued to be sprayed for five minutes while the substrate washeated. After that, similarly to the case described above, by performingthe heating for ten minutes using the infrared lamp heating apparatus,the substrate was dried.

FIG. 13 is SEM images of the obtained GZO films. When geometries of thesurfaces were observed using the SEM images, it was confirmed that theGZO film formed on the heated substrate lost smoothness of the surfacethereof.

FIG. 14 is a table for showing a relationship between the substratetemperature in the film formation and the surface resistance. As theheating temperature in the film formation rises, the surface resistancevalue considerably increases. Note that, when the heating temperature inthe film formation was 80° C., the surface resistance value was beyond adetection limit, and thus, the measurement was impossible.

EXAMPLE 6

A spin coater was used to uniformly apply the resist on the substrate.Exposure was performed with i-rays, and a pattern having a line andspace of 100 μm was formed. After that, a dip coater was used to apply3M_(TM)Novec_(TM)EGC-1720 (manufactured by 3M Japan Limited) as thewater repellent to the substrate. By peeling the resist, the substratehaving a desired water-repellent pattern formed thereon was obtained.Note that, as the substrate, a PET substrate was used.

Then, similarly to the case of Example 1, a water dispersion liquidcontaining ITO fine particles was put in the first chamber of the filmforming apparatus described above that did not have the mist trap, and avoltage of 2.4 MHz was applied by the ultrasonic vibrator (manufacturedby HONDA ELECTRONICS Co., LTD.) to generate the mist. The obtained mistwas sent to the vicinity of the substrate in the second chamber bycausing air to flow into the first chamber.

In the second chamber, the mist continued to be sprayed onto thesubstrate for five minutes under a state in which the substrate wastilted from the horizontal plane and the substrate was tilted from theplane orthogonal to the direction of the spraying of the mist. At thistime, the substrate was not heated, and the mist was sprayed at roomtemperature.

After that, an infrared lamp heating apparatus was used to heat thesubstrate at a temperature of 150° C. The heating was performed for tenminutes in a low vacuum of about 30 Pa. Subsequently thereto, after a UVray (mixture of 254 nm and 185 nm) was radiated to a surface of the filmformed on the substrate, similarly to the case described above, thesubstrate was set in the second chamber of the film forming apparatus,and the mist continued to be sprayed for five minutes. After that,similarly to the case described above, by performing the heating for tenminutes using the infrared lamp heating apparatus, the substrate wasdried.

FIG. 15 is a SEM image of the ITO film on the water-repellent patternedsubstrate. The ITO film was formed on a hydrophilic portion withoutbeing formed on a water-repellent portion.

As described above, when a metal oxide film was formed by spraying themist of the dispersion liquid containing the ITO fine particles, withthe usage of the water-repellent pattern, the metal oxide film in anintended pattern was selectively formed.

EXAMPLE 7

A spin coater was used to uniformly apply the resist on the substrate.Exposure was performed with i-rays, and a pattern having a line andspace of 100 μm was formed. After that, a dip coater was used to apply3M_(TM)Novec_(TM)EGC-1720 (manufactured by 3M Japan Limited) as thewater repellent to the substrate. By peeling the resist, the substratehaving a desired water-repellent pattern formed thereon was obtained.Note that, as the substrate, a PET substrate was used.

Then, similarly to the case of Example 3, a water dispersion liquidcontaining GZO fine particles was prepared and put in the first chamberof the film forming apparatus that did not have the mist trap, and avoltage of 2.4 MHz was applied by the ultrasonic vibrator (manufacturedby HONDA ELECTRONICS Co., LTD.) to generate the mist. The obtained mistwas sent to the vicinity of the substrate in the second chamber bycausing air to flow into the first chamber. In the second chamber, themist continued to be sprayed onto the substrate for five minutes under astate in which the substrate was tilted from the horizontal plane andthe substrate was tilted from the plane orthogonal to the direction ofthe spraying of the mist. At this time, the substrate was not heated,and the spraying was performed at room temperature.

After that, an infrared lamp heating apparatus was used to heat thesubstrate at a temperature of 150° C. The heating was performed for tenminutes in a low vacuum of about 30 Pa. Subsequently thereto, after a UVray (mixture of 254 nm and 185 nm) was radiated to a surface of the filmformed on the substrate, similarly to the case described above, thesubstrate was set in the second chamber of the film forming apparatus,and the mist continued to be sprayed for five minutes. After that,similarly to the case described above, by performing the heating for tenminutes using the infrared lamp heating apparatus, the substrate wasdried.

FIG. 16 is a SEM image of the GZO film on the water-repellent patternedsubstrate. It was confirmed that the state was different between thewater-repellent portion with water-repellent coating and the hydrophilicportion other than the water-repellent portion.

COMPARATIVE EXAMPLE 2

A spin coater was used to uniformly apply the resist on the substrate.Exposure was performed with i-rays, and a pattern having a line andspace of 100 μm was formed. After that, a dip coater was used to apply3M_(TM)Novec_(TM)EGC-1720 (manufactured by 3M Japan Limited) as thewater repellent to the substrate. By peeling the resist, the substratehaving a desired water-repellent pattern formed thereon was obtained.Note that, as the substrate, a PET substrate was used.

Similarly to the case of Example 1, a water dispersion liquid (NanoTekSlurry manufactured by C. I. Kasei Company, Limited) containing ITO fineparticles was prepared and put in the first chamber of the film formingapparatus described above that did not have the mist trap, and a voltageof 2.4 MHz was applied by the ultrasonic vibrator (manufactured by HONDAELECTRONICS Co.,LTD.) to generate the mist. The obtained mist was sentto the vicinity of the substrate in the second chamber by causing air toflow into the first chamber.

In the second chamber, a substrate heated to 60° C. and a substrateheated to 80° C. were set, and the mist continued to be sprayed to therespective substrates for five minutes. At this time, while the sprayingwas performed, the substrates were set under a state of being tiltedfrom the horizontal plane and being tilted from the plane orthogonal tothe direction of the spraying of the mist by 45 degrees. After that, aninfrared lamp heating apparatus was used to heat the substrate at atemperature of 150° C. The heating was performed for ten minutes in alow vacuum of about 30 Pa.

FIG. 17 is a SEM image of the substrate heated to 60° C. It is thoughtthat, the velocity of vaporization of the dispersion liquid containingthe metal oxide fine particles on the heated substrate is extremelyhigh, and thus, the dispersion liquid attached to the water-repellentportion was vaporized without being repelled. Therefore, it wasconfirmed that the metal oxide film of a very small quantity was formedeven in the water-repellent portion.

FIG. 18 is a SEM image of the substrate heated to 80° C. It wasconfirmed that the metal oxide film was formed entirely irrespective ofwhether on the hydrophilic portion or on the water-repellent portion. Asa result, patterning along a line was not obtained.

COMPARATIVE EXAMPLE 3

A spin coater was used to uniformly apply the resist on the substrate.Exposure was performed with i-rays, and a pattern having a line andspace of 100 μm was formed. After that, a dip coater was used to apply3M_(TM)Novec_(TM)EGC-1720 (manufactured by 3M Japan Limited) as thewater repellent to the substrate. By peeling the resist, the substratehaving a desired water-repellent pattern formed thereon was obtained.Note that, as the substrate, a PET substrate was used.

Similarly to the case of Example 1, a water dispersion liquid (NanoTekSlurry manufactured by C. I. Kasei Company, Limited) containing ITO fineparticles was prepared and put in the first chamber of the film formingapparatus described above that had the mist trap, and a voltage of 2.4MHz was applied by the ultrasonic vibrator (manufactured by HONDAELECTRONICS Co., LTD.) to generate the mist. The obtained mist was sentto the vicinity of the substrate in the third chamber by causing air toflow into the first chamber.

In the third chamber, the substrate was set so as to be in parallel withthe horizontal plane and so as to be in parallel with the planeorthogonal to the direction of the spraying of the mist, and the mistcontinued to be sprayed for five minutes. At this time, the substratewas not heated, and the spraying was performed at room temperature.

After that, an infrared lamp heating apparatus was used to heat thesubstrate at a temperature of 200° C. The heating was performed for tenminutes in a low vacuum of about 30 Pa. Subsequently thereto, after a UVray (mixture of 254 nm and 185 nm) was radiated to a surface of a filmformed on the substrate, similarly to the case described above, thesubstrate was set in the third chamber of the film forming apparatus.Note that, the substrate was set so as to be in parallel with thehorizontal plane and so as to be in parallel with the plane orthogonalto the direction of the spraying of the mist. After the mist continuedto be sprayed onto the substrate for five minutes, similarly to the casedescribed above, by performing the heating for ten minutes using theinfrared lamp heating apparatus, the substrate was dried.

FIG. 19 is a SEM image of the obtained ITO film. The metal oxide filmwas formed on the entire substrate almost irrespective of whether on thehydrophilic portion or on the water-repellent portion. This is thoughtto be because the dispersion liquid containing the metal oxide fineparticles that were attached to the water-repellent portion wasvaporized without being repelled. As a result, patterning along a lineas observed in Example 6 was not obtained.

Results of <Example 2> and <Comparative Example 1> are now discussed. Itwas found that, compared with a case in which the dispersion liquidcontaining the metal oxide fine particles was applied to the substrateby spin coating, when the film was formed by the film forming apparatususing the mist, the visible light transmittance was higher and the sheetresistance was lower. Further, it was found that, when the temperatureof the substrate in the film formation was 40° C. or lower, a suitablemetal oxide film having a low sheet resistance was obtained.

Further, results of <Example 1>, <Example 3>, and <Example 4> are nowdiscussed. A suitable metal oxide film was obtained both when the metaloxide fine particles were ITO and when the metal oxide fine particleswere GZO. Further, a suitable metal oxide film was obtained both whenthe dispersion medium was water and when the dispersion medium was IPA.

Results of <Example 6>, <Comparative Example 2>, and <ComparativeExample 3> are now discussed. By forming the water-repellent film, themetal oxide film suitably patterned by the film forming apparatus usingthe mist was obtained. At that time, when the substrate was heated to60° C. or higher, the metal oxide film was formed on the entire surfaceof the substrate, and it was difficult to form the pattern. Further, itwas found that, by tilting the substrate from the horizontal plane andtilting the substrate from the plane orthogonal to the direction of thespray in the film formation, the suitably patterned metal oxide film wasobtained.

What is claimed is:
 1. A method of manufacturing a thin film,comprising: generating mist of a dispersion liquid containing fineparticles; supplying the generated mist of the dispersion liquid onto asubstrate; and drying the dispersion liquid supplied onto the substrate.2. A method of manufacturing a thin film according to claim 1, whereinthe fine particles contained in the generated mist of the dispersionliquid each have a particle size of 100 nm or less.
 3. A method ofmanufacturing a thin film according to claim 1, wherein the substratecomprises a resin and has flexibility.
 4. A method of manufacturing athin film according to claim 1, wherein the drying the dispersion liquidis performed at a temperature that is lower than a softening point ofthe substrate.
 5. A method of manufacturing a thin film according toclaim 4, wherein the drying the dispersion liquid is performed at atemperature of 10° C. or higher and 40° C. or lower.
 6. A method ofmanufacturing a thin film according to claim 1, further comprising:forming, on the substrate, a hydrophilic/water-repellent patterncomprising a hydrophilic portion and a water-repellent portion, whereinthe supplying the generated mist is performed to the substrate havingthe hydrophilic/water-repellent pattern formed thereon in the forming ahydrophilic/water-repellent pattern.
 7. A method of manufacturing a thinfilm according to claim 1, further comprising, after the drying thedispersion liquid, radiating an ultraviolet ray to the substrate,wherein the supplying the generated mist is performed again to thesubstrate to which the ultraviolet ray is radiated in the radiating anultraviolet ray.
 8. A method of manufacturing a thin film according toclaim 7, wherein, in the supplying the generated mist, the fineparticles contained in the mist that is supplied before the radiating anultraviolet ray and the fine particles contained in the mist that issupplied after the radiating an ultraviolet ray are different.
 9. Amethod of manufacturing a thin film according to claim 7, wherein theultraviolet ray radiated in the radiating an ultraviolet ray at leasthas a wavelength of 200 nm or less.
 10. A method of manufacturing a thinfilm according to claim 1, wherein, in the supplying the generated mist,the substrate is tilted from a horizontal plane.
 11. A method ofmanufacturing a thin film according to claim 1, wherein, in thesupplying the generated mist, the substrate is tilted from a planeorthogonal to a direction of the supply.
 12. A method of manufacturing athin film according to claim 1, wherein the fine particles comprisemetal oxide fine particles comprising any one of indium, zinc, tin, andtitanium.
 13. A transparent conductive film, which is manufactured bythe method of manufacturing a thin film of claim 12.